Comb polymers for the hair

ABSTRACT

Utilisation of (meth)acrylic comb copolymers with side chains of the hydroxy and alkoxy polyalkylene glycol type in which are present both ethylene oxide and propylene oxide links. These copolymers give a styling effect and an elimination of rinsing. The invention also relates to a cosmetic formulation containing such structures as well as a hair treatment process based on this formulation.

Reference to Prior Applications

This application is a continuation application of U.S. application Ser.No. 13/415,001, filed Mar. 8, 2012, now allowed; and claims priority toU.S. provisional application Ser. No. 61/468,641, filed Mar. 29, 2011;and to French patent application 11 52530, filed Mar. 28, 2011, allincorporated herein by reference.

FIELD OF THE INVENTION

The present invention concerns the sector of additives used in cosmeticformulations intended to be applied to the scalp. It includes theutilization of (meth)acrylic comb copolymers with side chains of thehydroxy and alkoxy polyalkylene glycol type in which are present bothethylene oxide and propylene. These copolymers give the shampoos inwhich they are incorporated a styling effect and an elimination ofrinsing that is more pronounced than that of comb copolymersmanufactured from (meth)acrylic acid and side groups of the hydroxy ormethoxy polyethylene glycol (MPEG) type.

Additional advantages and other features of the present invention willbe set forth in part in the description that follows and in part willbecome apparent to those having ordinary skill in the art uponexamination of the following or may be learned from the practice of thepresent invention. The advantages of the present invention may berealized and obtained as particularly pointed out in the appendedclaims. As will be realized, the present invention is capable of otherand different embodiments, and its several details are capable ofmodifications in various obvious respects, all without departing fromthe present invention. In this regard, the description herein is to beunderstood as illustrative in nature, and not as restrictive.

BACKGROUND OF THE INVENTION

In the field of hair care, compositions based on anionic, non-ionic andamphoteric surfactants are commonly used. They are applied to wet hairand foam is generated by massage or friction with the hands whichallows, after rinsing with water, elimination of the dirt initiallypresent.

If these formulations have good washing power, their intrinsic cosmeticproperties however remain limited, particularly because of therelatively aggressive nature of the treatment to which they subject thehair: it can cause more or less marked damage to the capillary fibre,including the gradual elimination of lipids and proteins contained inthe hair.

It is also necessary to use additives whose function is to improve thecosmetic properties of the hair formulations in which they areincorporated. Among these properties, “the styling effect” is one thatis sought in particular: It occurs through an ease of styling andmaintenance of the hair after rinsing, and by a contribution to thevolume and lightness at the dry hair level.

To do this, for a long time, use has been made of cationic polymerswhich, because of their strong affinity for capillary fibre which isanionic in nature, will have a persistent effect on the hair.Nevertheless, this phenomenon can lead to product deposits that are toosignificant: The feel of the hair becomes laden, unpleasant; the hairbecomes stiff and there is an inter-fibre adhesion which affectsstyling.

A new generation of products has recently been developed to overcomethese disadvantages. It is based on comb structured (meth)acryliccopolymers. The use of these products for hair care was described indocuments EP 1 632 508 A1 and EP 2 168 991 A1. It will be apparent thattheir use in a shampoo formulation allows not only an improvement in itsstyling effect, but also facilitates its elimination after rinsing withwater.

The expression “(meth)acrylic comb copolymer” is intended to designate acopolymer consisting of a skeleton that is essentially linear and of a(meth)acrylic type on which are grafted at least 2 side segmentsconsisting of at least one “macromonomer”. The term “marcromonomer”refers to a water-soluble polymer or copolymer having at least oneterminal group with an unsaturated ethylene function.

In the case of products developed for hair care and described indocuments EP 1 632 508 A1 and EP 2 168 991 A1, this macromonomer is ofthe hydroxyl methacrylate or methoxy polyethylene glycol type (MPEG orMAMPEG methacrylate). In summary, the comb copolymers described in thesetwo documents are the result of the synthesis between a first anionicmonomer which can be (meth)acrylic acid, and an alkoxy or hydroxypolyakylene glycol macromonomer with the formula R—(EO)_(n)—R′, with:

-   -   EO designating ethylene oxide and n being an integer between 3        and 300,    -   R designating an unsaturated polymerizable function such as the        methacrylate function,    -   R′ representing hydrogen or a carbon radical with from 1 to 30        carbon atoms.

In these two documents will be noted all the importance given to thespecific macromonomers MPEG550 and MPEG2000, methoxypolyethylene glycolmethacrylate with a mean molar mass by weight equal to 550 g/mol and2,000 g/mol respectively.

SUMMARY OF THE INVENTION

Now, quite surprisingly, the inventors have developed the use of(meth)acrylic comb copolymers with a different structure that haveproven to be more efficient at the level of the hair styling effect andin terms of elimination by rinsing with water. These polymers comprise,consist essentially of, or consist of:

-   -   a) at least one monomer which is (meth)acrylic acid, and    -   b) at least one macromonomer with the formula (I):        R—(PO)_(m)-(EO)_(n)—R′  (I)        -   m and n are each non-zero integers less than 150,        -   PO and EO respectively designate propylene oxide and            ethylene oxide,        -   R designates a polymerizable unsaturated function,        -   R′ represents hydrogen or an alkyl group with from 1 to 4            carbon atoms.

In these polymers the monomers exist in polymerized form, but arenevertheless referred to as monomers in accord with convention.

These structures differ from those mentioned in documents EP 1 632 508A1 and EP 2 168 991 A1 in at least the sense that their macromonomercontains both ethylene oxide and propylene oxide links. There wasnothing to suggest that such a modification would impact in such abeneficial way the properties of styling effect and rinseability of theshampoos in which these polymers would be incorporated.

In addition, it is stated that the macromonomer of formula (I) is wellknown and described in patent U.S. Pat. No. 6,034,208. Also, themanufacture of the copolymers as indicated above, which are manufacturedfrom this macromonomer, is well known to the person skilled in the art,notably in a continuous, semi-continuous or batch process (see documentsU.S. Pat. Nos. 6,815,513, 6,214,958, 6,664,360 and 7,232,875). Finally,other uses of these structures were already known: notably as additivesin formulations of plaster (EP 1 377 533 A1, EP 1 615 860 A1), of cement(FR 2 939 128 A1 and FR 2 939 428 A1) or in paper coating dispersions(French application not yet published and filed under number FR 1054575).

A first object of the present invention is the use as a styling agent ina cosmetic formulation of at least one (meth)acrylic comb copolymer.These comb copolymers comprise, consist essentially of, or consist of:

-   -   a) at least one monomer which is (meth)acrylic acid, and    -   b) at least one macromonomer of formula (I):        R—(PO)_(m)-(EO)_(n)—R′  (I)        -   m and n are each non-zero integers less than 150,        -   PO and EO respectively designate propylene oxide and            ethylene oxide,        -   R designates a polymerizable unsaturated function,        -   R′ represents hydrogen or an alkyl group with from 1 to 4            carbon atoms.

This utilisation is also preferably characterized in that the(meth)acrylic comb copolymer comprises, consists essentially of, orconsists of, expressed as a percentage by weight of each of itscomponents:

-   -   a) from 5% to 30%, preferentially from 15% to 25% of at least        one monomer which is (meth)acrylic acid,    -   b) from 70% to 95%, preferentially from 75% to 85% of at least        one macromonomer with formula (I),    -   c) from 0% to 20%, preferentially from 0% to 10% of at least one        monomer which is an ester of (meth)acrylic acid, preferentially        ethyl acrylate,        where preferably the sum of the percentages a), b), and c) are        equal to 100%.

In a preferred embodiment, this utilisation is characterized in that Rdesignates the methacrylate or methacrylurethane function.

In a preferred embodiment, this use is characterized in that R′designates hydrogen.

In a preferred embodiment, this use is characterized in that n and m arebetween 10 and 90. Structures —(PO)_(m)-(EO)_(n)— designate both blockstructures as well statistical structures, and this is true for theentire Application.

In a preferred embodiment the (meth)acrylic comb copolymer presents amean molar mass by weight of between 20,000 g/mol and 6,000,000 g/mol,preferentially between 40,000 and 1,000,000 g/mol.

The (meth)acrylic comb copolymer can be obtained for example by freeradical polymerization in solution, in direct or inverse emulsion, insuspension or precipitation in solvents, in the presence of catalyticsystems and transfer agents, or even in a controlled radicalpolymerization and preferentially in polymerization controlled by anitroxides (NMP) or by cobaloxymes, in polymerization by atom transferradical polymerization (ATRP), by controlled radical polymerization bysulphur derivatives, selected from among the carbamates, dithioesters ortrithiocarbonates (RAFT) or the xanthates.

It may be fully or partially neutralized by one or more neutralizingagents with a monovalent or polyvalent cation, the said agents beingpreferentially being selected from ammonium hydroxide or among thehydroxides and/or oxides of calcium, magnesium, or among the hydroxidesof sodium, potassium, lithium, or among the primary, secondary ortertiary aliphatic and/or cyclic amines such as preferentiallystearylamine, ethanolamines (mono-, di-, triethanolamine), mono anddiethylamine, cyclohexylamine, methylcyclohexylamine, amino methylpropanol, morpholine, and preferentially in that the neutralizing agentis chosen from among triethanolamine and sodium hydroxide.

It can also be separated into several phases according to static ordynamic processes by one or more polar solvents preferentially belongingto the group consisting of water, methanol, ethanol, propanol,isopropanol, the butanols, acetone, tetrahydrofuran or their mixtures.

This utilisation is also characterized in that the cosmetic formulationpreferably comprises from 0.01% to 50%, more preferentially from 0.1% to30%, very preferentially from 3% to 20% by dry weight of the saidcopolymer with respect to its total weight.

This utilisation is also preferably characterized in that theformulation includes at least one constituent chosen from among water,hydrophilic organic solvents and preferentially alcohols, preferentiallymonoalcohols, linear or branched in C1-C6 and polyols and glycol ethers,preferentially in C2, and aldehydes in C2-C4 hydrophylic, waxes, pastyfats, gums and their mixtures, of animal, vegetable, mineral orsynthetic origin, lipophilic organic solvents, oils of animal,vegetable, mineral or synthetic origin, synthesis esters and ethers,pentaerythritol esters, the fatty alcohols with 12 to 26 carbon atoms,fluorinated oils, partially hydrocarbonated and/or siliconated,siliconated oils, volatile or not, linear or cyclical, liquid or pastyat room temperature, pigments, nacres, fillers, water-soluble dyes,fat-soluble dyes, filmification agents, surfactants, vitamins, perfumes,nacrating agents, thickeners, gelling agents, trace elements, softeners,retention aids, perfumes, alkalinizing or acidifying agents,preservatives, solar filters, anti-oxidants, the anti hair loss agents,anti-dandruff agents, propellant agents, ceramides and their mixtures.

This utilisation is also preferably characterized in that theformulation presents in the form of a capillary composition,preferentially for the maintenance of hair styling or the shaping ofhair, very preferentially in the form of shampoos, gels, waving lotions,brushing lotions, of setting and styling compositions chosen from thelacquers or sprays, after-shampoos whether rinsed or not, compositionsfor permanents, straightening, dyeing or bleaching or again, in the formof compositions for rinsing, for application before or after a dyeing, ableaching, a permanent or a straightening, or again between the twosteps of a permanent or a straightening.

Another object of the present invention consists of a cosmeticformulation comprising at least one (meth)acrylic comb copolymer thatcomprises, consists essentially of, or consists of:

-   -   a) at least one monomer which is (meth)acrylic acid, and    -   b) at least one macromonomer with the formula (I):        R—(PO)_(m)-(EO)_(n)—R′  (I)        -   m and n are each non-zero integers less than 150,        -   PO and EO respectively designate propylene oxide and            ethylene oxide,        -   R designates a polymerizable unsaturated function,        -   R′ represents hydrogen or an alkyl group with from 1 to 4            carbon atoms.

This formulation is also preferably characterized in that the(meth)acrylic comb copolymer comprises, consists essentially of, orconsists of, expressed as a percentage by weight of each of itscomponents:

-   -   a) 5% to 30%, preferentially of 15% to 25% of at least one        monomer which is (meth)acrylic acid,    -   b) 70% to 95%, preferentially of 75% to 85% of at least one        macromonomer with formula (I),    -   c) 0% to 20%, preferentially of 0% to 10% of at least one        monomer which is an ester of (meth)acrylic acid, preferentially        ethyl acrylate,        the sum of the percentages a), b), and c) preferably being equal        to 100%.

In a preferred embodiment, this formulation is characterized in that forthe said copolymer, R designates the methacrylate or methacrylurethanefunction.

In a preferred embodiment, this formulation is characterized in that forthe said copolymer, R′ designates hydrogen.

In a preferred embodiment, this formulation is characterized in that forthe copolymer, n and m are between 10 and 90.

This formulation is also preferably characterized in that for thecopolymer it presents a mean molar mass by weight of between 20,000g/mol and 6,000,000 g/mol, preferentially between 40,000 g/mol and1,000,000 g/mol.

This formulation is also preferably characterized in that the cosmeticformulation comprises from 0.01% to 50%, more preferentially from 0.1%to 30%, very preferentially from 3% to 20% by dry weight of the saidcopolymer with respect to its total weight.

This formulation is also preferably characterized in that it includes atleast one constituent chosen from among water, hydrophilic organicsolvents and preferentially alcohols, preferentially monoalcohols,linear or branched in C1-C6 and polyols and glycol ethers,preferentially in C2, and aldehydes in C2-C4 hydrophylic, waxes, pastyfats, gums and their mixtures, of animal, vegetable, mineral orsynthetic origin, lipophilic organic solvents, oils of animal,vegetable, mineral or synthetic origin, synthesis esters and ethers,pentaerythritol esters, the fatty alcohols with 12 to 26 carbon atoms,fluorinated oils, partially hydrocarbonated and/or siliconated,siliconated oils, volatile or not, linear or cyclical, liquid or pastyat room temperature, pigments, nacres, fillers, water-soluble dyes,fat-soluble dyes, filmification agents, surfactants, vitamins, perfumes,nacrating agents, thickeners, gelling agents, trace elements, softeners,retention aids, perfumes, alkalinizing or acidifying agents,preservatives, solar filters, anti-oxidants, the anti hair loss agents,anti-dandruff agents, propellant agents, ceramides and their mixtures.

This formulation is also preferably characterized in that it presents inthe form of a capillary composition, preferentially for the maintenanceof hair styling or the shaping of hair, very preferentially in the formof shampoos, gels, waving lotions, brushing lotions, of setting andstyling compositions chosen from the lacquers or sprays, after-shampooswhether rinsed or not, compositions for permanents, straightening,dyeing or bleaching or again, in the form of compositions for rinsing,for application before or after a dyeing, a bleaching, a permanent or astraightening, or again between the two steps of a permanent or astraightening.

Another object of the present invention is a cosmetic hair treatmentprocess characterized in applying to the hair a cosmetic formulation asdefined above. As used herein, hair includes human hair. Preferably thehair is wet prior to application.

The following examples will allow a better understanding of theinvention, without however limiting its scope.

EXAMPLES

A shampoo composition is prepared that comprises the followingcomponents (in weight %):

-   -   7.5% of lauryl ether sulphate,    -   2.5% of coconut betaine amphoteric surfactant (Dehyton AB30 from        Cognis™)    -   5% of coconut polyglucoside surfactant (Plantacare 818 UP from        Cognis™)    -   3% (by dry weight) of the polymer to be tested,    -   QS 100% water        Test No. 1

This test demonstrates the prior art, and implements a copolymerconsisting of, expressed in % by weight of each of its monomers:

-   -   a) 20% methacrylic acid,    -   b) 80% of a macromonomer with formula (I):        R—(PO)_(m)-(EO)_(n)—R′  (I)        -   m=0, n=48,        -   PO and EO respectively designate propylene oxide and            ethylene oxide,        -   R designates the methacrylate function,        -   R′ represents the methyl radical.            totally neutralized by sodium hydroxide and with a mean            molecular mass by weight equal to 25,000 g/mol.

Macromonomer (I) is thus here MPEG methacrylate with a mean molar massequal to 2,000 g/mol (illustrated in documents EP 1 632 508 A1 and EP 2168 991 A1).

Test No. 2

This test demonstrates the prior art, and implements a copolymerconsisting of, expressed in % by weight of each of its monomers:

-   -   a) 20% methacrylic acid,    -   b) 80% of a macromonomer with formula (I):        R—(PO)_(m)-(EO)_(n)—R  (I)        -   m=0, n=110,        -   PO and EO respectively designate propylene oxide and            ethylene oxide,        -   R designates the methacrylate function,        -   R′ represents the methyl radical,            totally neutralized by sodium hydroxide and with a mean            molecular mass by weight equal to 60,000 g/mol.

Macromonomer (I) is thus here MPEG methacrylate with a mean molar massby weight equal to 5,000 g/mol.

Test No. 3

This test demonstrates the invention, and implements a copolymerconsisting of, expressed in % by weight of each of its monomers:

-   -   a) 20% methacrylic acid,    -   b) 80% of a macromonomer with formula (I):        R—(PO)_(m)-(EO)_(n)—R′  (I)        -   m=15, n=46,        -   PO and EO respectively designate propylene oxide and            ethylene oxide,        -   R designates the methacrylate function,        -   R′ represents the hydroxy radical,            totally neutralized by sodium hydroxide and with a mean            molecular mass by weight equal to 60,000 g/mol.

In humid and thy environments, good untangling properties and animproved styling in the case of the polymer No. 3 according to theinvention are observed. It is also apparent there is a more pronouncedcapacity of this polymer to be eliminated by rinsing the hair in water.

The above written description of the invention provides a manner andprocess of making and using it such that any person skilled in this artis enabled to make and use the same, this enablement being provided inparticular for the subject matter of the appended claims, which make upa part of the original description.

As used herein, the words “a” and “an” and the like carry the meaning of“one or more.” The phrases “selected from the group consisting of,”“chosen from,” and the like include mixtures of the specified materials.Terms such as “contain(s)” and the like are open terms meaning‘including at least’ unless otherwise specifically noted.

All references, patents, applications, tests, standards, documents,publications, brochures, texts, articles, etc. mentioned herein areincorporated herein by reference. Where a numerical limit or range isstated, the endpoints are included. Also, all values and subrangeswithin a numerical limit or range are specifically included as ifexplicitly written out.

The above description is presented to enable a person skilled in the artto make and use the invention, and is provided in the context of aparticular application and its requirements. Various modifications tothe preferred embodiments will be readily apparent to those skilled inthe art, and the generic principles defined herein may be applied toother embodiments and applications without departing from the spirit andscope of the invention. Thus, this invention is not intended to belimited to the embodiments shown, but is to be accorded the widest scopeconsistent with the principles and features disclosed herein. In thisregard, certain embodiments within the invention may not show everybenefit of the invention, considered broadly.

The invention claimed is:
 1. A cosmetic formulation for treating haircomprising a (meth)acrylic comb copolymer, said comb copolymercomprising: a) at least one (meth)acrylic acid monomer; and b) at leasttwo macromonomers of formula (I):R—(OCH₂—CH(CH₃))_(m)(OCH₂CH₂)_(n)—R′  (I) wherein variables m and n areintegers between 10 and 90; wherein —(OCH₂—CH(CH₃))_(m)(OCH₂CH₂)_(n)—include block and statistical structures; wherein R designates apolymerizable unsaturated function; wherein R′ is a hydrogen atom, or analkyl group having from 1 to 4 carbon atoms; wherein at least two sidechains of the comb copolymer comprise the—(OCH₂—CH(CH₃))_(m)(OCH₂CH₂)_(n)—R′ segment of formula (I); wherein the(meth)acrylic acid monomers are 5% to 30% by weight of the comb polymer;and wherein the macromonomers of formula (I) are 70% to 95% by weight ofthe comb copolymer.
 2. The cosmetic formulation according to claim 1,wherein the (meth)acrylic comb copolymer comprises, expressed as apercentage by weight of each of its components: a) 15% to 25% of(meth)acrylic acid, b) 75% to 85% of a macromonomer with formula (I),and c) 0% to 20% of a monomer which is an ester of (meth)acrylic acid,the sum of the percentages a), b), and c) being equal to 100%.
 3. Thecosmetic formulation according to claim 1, wherein R′ is a hydrogenatom.
 4. The cosmetic formulation according to claim 1, wherein thecopolymer has a mean molar mass by weight of 20,000 g/mol-6,000,000g/mol.
 5. The cosmetic formulation according to claim 1, wherein thecosmetic formulation comprises from 0.01% to 50% of said copolymer withrespect to its total weight.
 6. The cosmetic formulation according toclaim 5, wherein the cosmetic formulation comprises from 3% to 20% ofsaid copolymer with respect to its total weight.
 7. The cosmeticformulation according to claim 1, wherein the cosmetic formulationfurther comprises at least one constituent chosen from water,monoalcohols, linear or branched in C1-C6 and polyols, glycol ethers,waxes, pasty fats, gums, oils of animal, vegetable, mineral or syntheticorigin, pentaerythritol esters, fatty alcohols with 12 to 26 carbonatoms, fluorinated oils, partially hydrocarbonated and/or siliconated,siliconated oils, pigments, nacres, fillers, water-soluble dyes,fat-soluble dyes, filmification agents, surfactants, vitamins, perfumes,nacrating agents, thickeners, gelling agents, trace elements, softeners,retention aids, perfumes, alkalinizing agents, acidifying agents,preservatives, solar filters, anti-oxidants, anti hair loss agents,anti-dandruff agents, propellant agents, ceramides, and mixturesthereof.
 8. The cosmetic formulation according to claim 1, wherein thecosmetic formulation is a shampoo, gel, waving lotion, brushing lotion,setting and styling composition chosen from lacquers and sprays,after-shampoo whether rinsed or not, or is a composition for permanents,straightening, dyeing or bleaching.
 9. The cosmetic formulationaccording to claim 1, wherein the cosmetic formulation is a compositionfor rinsing or for application before or after a dyeing.
 10. A method,comprising applying the cosmetic formulation according to claim 1 tohair.
 11. The method of claim 10, comprising applying the cosmeticformulation to wet hair.
 12. The cosmetic formulation according to claim1, wherein R is a methacrylate function.
 13. The cosmetic formulationaccording to claim 1, wherein R is a methacrylurethane function.